DE2716155A1 - PHOTOGRAPHIC RECORDING MATERIAL FOR THE COLOR DIFFUSION TRANSFER PROCESS - Google Patents

Description

PATENT LAWYERS

Γ Dr-Ing. Wom

H.Bartets

2716155 DW.-Chem. Dr. Brandes

Dr-InQ. hero CHpL-Phye. WoHf

8 Munich 22. TiechalBe 8

Tel. (089) 293297 Telex 05 23325 (patwo d) telegram address: wotffpatent, some

Postal check account Stuttgart 7211

(BLZ 6OO WO 7O)

Deutsche Bank AG, M / 28630 (BLZ 60070070) Office hours: 8 a.m. to 12 p.m. 1-4.30 p.m. except Saturdays

February 24 , 1977 25/93 Reg. No. 125 239

Eastman Kodak Company, 343 State Street, Rochester,
New York State, United States of America

Photographic recording material for the
Color diffusion transfer process

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Photographic material for the color diffusion transfer process.

The invention relates to a photographic recording material for the color diffusion transfer process with:

a) at least one applied to a layer support, light-sensitive silver halide emulsion layer, which has a Contains an image dye-providing compound or is in contact with a layer containing such a compound,

b) an image receiving layer,

c) a rupturable container with an alkaline developing liquid and

d) a silver halide developing agent.

For the implementation of the color diffusion transfer process, e.g. from US Pat. In the case of recording materials with an integrated image-receiving layer, the image-receiving layer remains permanent with the recorded photographic image connected to the image-generating layers and auxiliary layers, if a transparent support is on the observer's side of the recording material is used. The color image settles composed of dyes that are generated in image-forming units and through the layers of the recording material are diffused to the image receiving layer. After exposure of such a recording material, an alkaline developing liquid dispersed in the recording material permeates the various densities initiating the development of the exposed, light-sensitive silver halide emulsion layers. The emulsion layers are developed in proportion to the extent of exposure and the image dyes produced, which are in the

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corresponding image-forming layers generated or released begin to diffuse through the layer structure of the recording material. At least part of the picture-wise Distribution of released diffusible dyes then diffuses into the image receiving layer, in which an image of the original is produced.

In addition to recording materials with an integrated image-receiving layer, recording materials have also become known, in which the image-receiving part is separated from the photosensitive part after the development process has been carried out and the dyes have been transferred to the image-receiving layer. Recording material / of this type are for example from US-PS 2,983,606, 3,362,819 and 3,362,821 are known.

When using such recording materials, especially when using recording materials with an integrated image receiving layer, the following problem has arisen:

After developing a recording material of the described Type may require a longer period of time, for example up to about 30 days, for the recording material is "dry". The reason why it takes a comparatively long time for the recording material to dry is because of this can be seen that the solvent, usually water, the developing liquid slowly out of the recording material evaporates, either through the edges of the recording material representing a pack or through the side parts, through which exposure was made and the image produced is viewed. These side parts of the recording material exist in generally made of a material that is comparatively impermeable to water vapor, for example poly (ethylene terephthalate). During the period in which the recording material is still damp or wet, inorganic salt crystals can form, that can grow slowly. Especially when calcium and sulfate ions are present, for example as impurities with the gelatin, an opaque one containing, for example, carbon black

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Layer, the support and / or the alkaline developing liquid can be carried over can be compared form large crystals of complex salts, mostly composed of calcium sulfate. These crystals do not show up immediately after the development process has been carried out, but only occur when the recording material dries. By crystal formation and thinning of the recording material physical defects or uneven areas are easily visible through the drying process. These defects can for example, have the shape of small spots or bulges that are irregularly distributed over the entire image area.

The object of the invention was to provide a recording material for the Indicate color diffusion transfer method, which of the described Disadvantages is free.

The invention was based on the knowledge that the task at hand can be solved by adding the alkaline developing liquid an alkali metal fluoride or alkali metal oxalate clogs.

The invention accordingly provides a photographic recording material for the color diffusion transfer process with:

a) at least one light-sensitive layer applied to a layer support A silver halide emulsion layer containing or having an image dye-providing compound Layer is in contact with such a compound,

b) an image receiving layer,

c) a splittable container with an alkaline developing liquid with a pH value of preferably at least 11, and

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d) a silver halide developer compound,

which is characterized in that the alkaline developing liquid contains an alkali metal fluoride or alkali metal oxalate.

If appropriate, mixtures of the alkali metal salts can also be used will.

The alkali metal salt or salts can be used together with the other conventional components for the preparation of the alkaline developing liquid. On the other hand, however, it is too possible to generate the alkali metal salt "in situ", e.g. by using the anion of the developing liquid in the form of an acid, an ester or an alkyl fluoride is added, wherein in the presence of excess alkali or base, e.g. KÜH, an alkali metal salt of the specified properties is produced.

Although the mechanism of action that of the present invention is not yet fully clarified, it is assumed that the anion of the salt is the one that is not present in the development tank Calcium binds and prevents the formation of calcium sulfate.

The most favorable anion in the individual case depends on the amounts of existing Impurities, the final pH value of the recording material and a subjective assessment of whether the crystalline Impurities that form, are objectionable from the viewer's point of view or not.

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For example, calcium carbonate is formed at a pH of 9.0 preferably over calcium sulfate because of the relative solubilities of these two salts. However, since calcium carbonate becomes soluble under the conditions of the development process below pH 6.0, forms at a pH below about 6.3, preferably calcium sulfate in relation to calcium carbonate. Is therefore the final pH value of the developed recording material is more than 6.3, an alkali metal carbonate can advantageously be used will. In contrast, is the final pH of the recording material below 6.3, other anions may be more advantageous. If the final pH value of the recording material is above 5.3, for example, alkali metal phosphates can also be advantageous.

Among other things, crystals other than calcium sulfate crystals are produced the suitability of a particular anion depends on whether the crystals produced using that anion are objectionable are or not. In general, such crystals or precipitates that can form should, in relative terms, be of smaller particle size, do not ripen to larger particles, as is the case with calcium sulfate crystals, for example is the case, which lead to the defects described and are not visible in the image receiving layer.

The use of alkali metal fluorides and alkali metal oxalates has proven to be particularly advantageous when the L ^: nd pH value of the recording material is about 4.5. At such a pH value, the precipitated calcium fluoride or calcium oxalate, which is formed preferentially over calcium sulfate, has a comparatively small particle size and does not produce any spots or defects that can be perceived by the naked eye.

The alkali metals of the alkali metal salts are those of the first group

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of the periodic system of the elements, namely lithium, sodium, Potassium, rubidium and cesium.

Particularly advantageous results are obtained when using potassium salts.

The alkali metal salts can be used in various concentrations. It has proven to be advantageous to use the salts in a concentration of about 0.01N to about 0.5N, in particular in concentrations of 0.05N to 0.2N.

The use of fluoride salts in photographic processes is known per se. Reference is made, for example, to the methods known from U.S. Patents 2,697,036, 2,706,157, 3,351,465 and 3,706,561. It is also already known to use a comparatively low level of potassium fluoride in activator solutions pH value to use for the development of recording materials for the diffusion transfer process. Is referred for example to US Pat. No. 3,260,598. In none of the patents mentioned are fluoride salts in the invention Wise used, nor is the problem underlying the present invention solved in the case of the patent specifications mentioned.

The recording material according to the invention can advantageously have a structure as is known from CAPS 928 559, for example. In the case of such a recording material, the support of the photosensitive part is or Element of the recording material transparent. The following are applied to the transparent substrate: an image receiving layer, a light-reflecting layer, an opaque layer and at least one light-sensitive layer containing or having a layer with an image dye-providing compound Connection is in contact. Adjacent to the top layer of the photosensitive part and adjacent to a transparent one Cover sheet is a splittable agent with alkaline developing liquid and an opacifying compound or a

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Opacifiers, such as carbon black, arranged. The cover sheet consists of a transparent layer support that is attached to a neutralizing layer and a control or delay layer is coated. That from such a "film unit" existing recording material can pass through a camera the transparent cover sheet exposed and pulled out of the camera through the gap formed by two pressure-exerting members will. In the process, these pressure-exerting members break open the container, so that the developing liquid contained in the container along with the opacifying agent is generated over the image May pour part of the material and protect it from further exposure. The developing liquid then develops the silver halide emulsion layers to produce image dyes which diffuse into and into the image receiving layer create a laterally correct image, which through the transparent layer support through on the opaque reflective layer as Background can be viewed. Further details can be found in the aforementioned CA-PS 928 559.

In an advantageous manner, the recording material according to the invention can furthermore have, for example, a structure as is known from US Pat. No. 3,415,644. In this case, the negative part of the material consists of an opaque layer support on which the light-sensitive layers and the layers that supply the associated image dyes are applied. Adjacent to the top layer and a transparent image receiving part is a splittable container with alkaline developing liquid, TiO ₂ and an indicator dye (see US Pat. No. 3,647,437). The image receiving part consists of a transparent support which is coated with a neutralizing layer, a control or retardation layer and an image receiving layer. The recording material forming a "film unit" is exposed in a camera through the transparent image receiving part and then pulled out of the camera through the gap formed by two pressure-exerting members. The splittable container is broken open so that its contents, consisting of developing _{liquid, TiO 2} and indicator dye, can pour over the image dye-producing part, and this

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protects against further exposure. The developing liquid in turn develops the silver halide emulsion layers to produce image dyes which diffuse into the image receiving layer, which can be viewed through the transparent support on a white background. The indicator dye is converted into a colorless form when the alkali is used up by the neutralizing layer. Further details regarding the structure of this recording material can be found in US Pat. No. 3,415,644. Since the image formed using such a recording material is reversed, an image reversing optical system such as a mirror system is required in the camera to reverse the reversed image so that a reversed image can be viewed through the image receiving layer.

In an advantageous manner, the recording material according to the invention can furthermore have, for example, a structure such as He from U.S. Patents 3,362,819, 3,415,645, 3,415,646, 2,983,606, 2,543,181, 3,647,437 and 3,635,707 and British Patent 1,330,524 and CA-PS 674 082 is known.

The recording material according to the invention can be used for the purpose of Development or, for the purpose of initiating development, treated with an alkaline developing liquid according to the usual known procedures. In an advantageous manner the developing liquid is supplied from a splittable container. The developing liquid advantageously contains a developing agent. If the developer bond is accommodated in the photosensitive recording material, the alkaline developing liquid serves to activate the developer compound present in the recording material.

The compounds providing image dyes used to produce a recording material according to the invention are they are those that are either (1) initially soluble or diffusible in the developing liquid and imagewise as

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Function of the development process made non-diffusible as described in more detail, for example, in U.S. Patents 2,647,049, 2,661,293, 2,698,244, 2,698,798, 2,802,735, 2,774,668 and

2,983,606 or (2) insoluble or nondiffusible in the developing liquid from the start Compounds that are made to diffuse imagewise as a result of the development process, such as are known are from U.S. Patents 3,227,550, 3,227,551, 3,227,552, 3,227,554,

3,243,294 and 3,445,228. These compounds can be preformed dyes or so-called dye precursors act, for example color couplers or so-called oxichromogenic compounds.

According to a particularly advantageous embodiment of the invention consists of the compounds which provide an image dye of non-diffusing, at least one ballast group containing image dye releasing compounds. These compounds are those that can be oxidized by oxidized developer compounds to compounds which, as a result of oxidation, have a diffusing Release dye, for example after alkali-induced hydrolysis. Such dye-releasing compounds are for example from U.S. Patents 3,725,062, 3,698,897, 3,628,952, 3,443,939, 3,443,940, 3,928,312, 3,929,760, 3,942,987 and 3,932,380, also the known US patent application B-351 673 and BE-PS 788 268, 825 215, 810 195 and 834 143, the DT-OS 24 06 664 and the US patent applications with the serial numbers 590 899 and 589 977 known.

According to a particularly advantageous embodiment of the invention are used as image dyes for the production of a recording material supplying compounds sulfonamido compounds containing ballast groups used, which can be split up by the action of alkali after oxidation and a diffusing one Release dye. Such, at least one ballast group having Sulfonamido compounds can be represented by the following formula:

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NHSO ₂ color

where mean:

a) stain a dye or dye precursor residue;

b) ballast an organic ballast group of such a molecular size and configuration (e.g. simple organic radicals or polymeric radicals) which the compound in the recording material during the development process in an alkaline developing liquid at a pH of at least about not makes diffusing;

c) G is a radical of the formula -OR or -NHR., in which: R is Hydrogen atom or a hydrolyzable radical and R- a hydrogen atom or an optionally substituted alkyl radical with 1 to 22 carbon atoms, e.g. a methyl, ethyl, hydroxyethyl, propyl, butyl, sec-butyl, tert-butyl, Cyclopropyl, 4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, Cyclohexyl, octyl, decyl, octadecyl, docosyl, benzyl or Phenethyl radical (if R. has the meaning of an alkyl radical with more than 6 carbon atoms, R. can also use part or all of the Represent ballast group);

d) Y the atoms required to complete a benzene, naphthalene or 5- to 7-membered heterocyclic ring, for example the atoms required to complete a pyrazolone or pyrimidine ring, and

e) N is a positive number of 1 or 2, where η is 2 when G is a radical of the formula -OR or when R- is a hydrogen atom or an alkyl radical with fewer than 8 carbon atoms.

According to a further advantageous embodiment of the invention, compounds which provide diffusible image dyes are first used to produce the recording material, for example so-called dye developer compounds, including so-called

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called color developing agents which form metal complexes, such as they are known, for example, from U.S. Patents 3,453,107, 3,544,545, 3,551,406, 3,563,739, 3,597,200 and 3,705,184 or so-called oxichromogenic developer compounds such as those described in greater detail in U.S. Patents 3,880,658, 3,854,945 and 3,791,827. In the case of the use of oxichromogenic developer compounds, the dye images are produced in that the oxichromogenic developer compounds diffuse into the image-receiving layer, in which they undergo chromogenic oxidation with formation subject to an image dye.

The recording material according to the invention can consist of a recording material for the production of positive monochrome images as well as positive multicolored images. In the case of a three-color system, the recording material has several silver halide emulsion layers to which image dyes form Compounds are assigned with a predominant spectral absorption within the range of the visible spectrum to which the silver halide emulsion layers are sensitive. This means that the blue-sensitive silver halide emulsion layer is assigned a compound which provides a yellow image dye, the green-sensitive silver halide emulsion layer a magenta image dye providing compound and the red sensitive silver halide emulsion layer a cyan image dye providing compound. The word "assigned" means that the individual image dye-providing compounds can be present in the silver halide emulsion layers themselves or in layers adjacent thereto.

üie optimal concentration of the image dye-providing compounds in the recording material can be very different, depending according to the compound used in the individual case and the results that are to be achieved. For example, the image dyes Forming compounds are processed starting from coating solutions in which the ratio of image dye-forming compound to hydrophilic film-forming binder is about 0.25 to about 4. The hydrophilic film-forming

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Binder, for example from one of the usual natural ones Binders or synthetic polymeric binders consist, for example, of gelatin or polyvinyl alcohol, which is permeable to aqueous alkaline developing liquids.

For the production of the recording materials according to the invention a variety of commonly known silver halide developing agents can be used, depending on the chemical System on which the recording material to be developed is based.

Examples of developer compounds that turn out to be more advantageous Suitable ways for the production of a photographic recording material according to the invention are:

Hydroquinone N-methylaminophenol

Ϊ-phenyl-3-pyrazolidinone

1-phenyl-4,4-dimethyl-3-pyrazolidinone

Aminophenols

N, N-diethyl-ε-phenylenediamine 3-methyl-N, N-diethyl-p-phenylenediamine N, N, N ¹ , N ¹ -tetramethyl-p-phenylenediamine 4-hydroxymethyl-4-methyl-1-phenyl-3 -pyrazolidinone and 4,4-bis (hydroxymethyl) -1-phenyl-3-pyrazolidinone.

When using image dye releasing compounds of the type described, the generation of diffusible image dyes is a function of the process of developing silver halide emulsions with a silver halide developing agent producing either negative or direct positive silver images in the emulsion layers. The silver halide emulsion layers provide direct positive silver images, for example when using direct positive silver halide emulsions of the internal image type or when using solarizing emulsions, which can be developed in the non-exposed areas, positive images are obtained in the image-receiving layer if

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Compounds which provide image dyes are used Release dyes when oxidized.

In the case of such a recording material, penetrates Exposure to alkaline developing liquid covers the various layers while initiating the development process. The developing agent present develops each of the silver halide emulsion layers in the unexposed areas (since the silver halide emulsion layers are direct positive Are emulsion layers) wherein the developing agent is oxidized imagewise, corresponding to the unexposed areas of the direct positive silver halide emulsion layers. The oxidized developing agent oxidizes the image dye releasing agent A compound which, in its oxidized form, undergoes a base-catalyzed reaction in which a preformed dye or dye precursor compound is imagewise released as a function of the imagewise exposure of the silver halide emulsion layers. At least some of the diffusible dyes or dye precursor compounds produced in an imagewise distribution then diffuses into the image-receiving layer producing a positive image of the original artwork.

Silver halide emulsions of the inner cavity type, which are advantageously suitable for the production of photographic recording materials according to the invention, are direct-positive emulsions, which provide latent images predominantly in the interior of the silver halide grains, as opposed to silver halide grains which provide the latent ones Deliver images predominantly on their surface. Such internal image type silver halide emulsions are, for example, from U.S. Patents 2,592,250, 3,761,276, 3,761,266, 3,761,267 and 3,703,584 are known. Such internal image type silver halide emulsions are characterized by the increased maximum density obtained when developed into negative silver images with "internal image type" developers as compared to Density obtained when developed with "surface-type" developers.

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Particularly advantageous silver halide emulsions of the internal image type are those which, when a sample amount of the silver halide emulsion is applied to a transparent layer support and when the recording material obtained in this way is exposed to a light intensity scale for a certain period of time between 0.01 and 1 second and 3 For minutes in a developer A of the composition given below (ie a developer of the inner image type), a maximum density which is at least 5 times as large as the maximum density which is obtained when an in the same manner expo ned recording material for 4 minutes at 20 ⁰ C in a developer B of the composition indicated below (ie, a developer surface type) is developed. The maximum density when using developer A is preferably at least O ₁ S density units greater than the maximum density when using developer D.

Developer A Hydroquinone 15 g Nonomethyl p-aminophenol sulfate 15 g

Sodium sulfite (dehydrated) 50 g

Potassium bromide 10 g Sodium hydroxide 25 g

Sodium thiosulphate 20 g Make up to 1 liter with water.

Developer B

p-hydroxyphenyl glycine 10 g

Sodium carbonate 100 g

Made up to 1 liter with water.

When silver halide emulsions of the internal image type are developed in the presence of a fogging agent or a nucleating agent, direct-positive silver images are obtained. Such a procedure has proven to be particularly advantageous.

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Suitable fogging agents are, for example, hydrazines, e.g. of the type known from U.S. Patents 2,588,982 and 2,563,785, hydrazides and hydrazones, e.g., of the type known from U.S. Patent 3,227,552, quaternary salts consisting of hydrazones, e.g. British Patent 1,283,835 and U.S. Patent 3,615,615, polymethine dyes containing hydrazone groups, such as that of U.S. Patent No. 3,615,615 3,718,470 of the known type and acylhydrazinophenylthioureas and mixtures of such compounds. The optimal one in each individual case The amount of abrasive can vary widely. It has generally proven advantageous to use the fogging agents in concentrations of about 0.4 to about 8 g per mole of silver of the photosensitive layer, provided that the fogging agent is in the Emulsion layer is applied or in concentrations of about 0.1 to about 2 g per liter of developer, provided that Fogging agent is applied in the developer solution. In the case of using fogging agents of the type known from U.S. Patents 3,615,615 and 3,718,470, the fogging agents are preferably used in concentrations of 50 to 400 mg per mole Silver photosensitive layer applied.

Advantageously, for the production of the invention Recording materials also use direct positive emulsions with their silver halide grains on their surface either chemically or by exposure to fog to allow development to maximum density without exposure. When exposed, the exposed areas are not developed, whereby an image resolution and a positive image are obtained. Silver halide emulsions of this type are disclosed, for example, in U.S. Patents 3,367,778, 3,501,305, 3,501,306 and US Pat 3 501 307 known.

Finally, for the production of a recording material according to the invention in an advantageous manner also direct-peeitive Emulsions of the type described, for example, in the book by Mees and James, "The Theory of the Photographic Process", published by MacMillan Co., New York, N.Y., 1966, pp. 149-167 is known.

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In the case of a multicolored recording material, the various silver halide emulsion layers can be arranged on the support in a conventional manner, i.e. the The blue-sensitive silver halide emulsion layer is the first layer on the exposure side, followed by the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. If necessary, a yellow dye layer or a yellow colloidal silver-containing layer between the blue-sensitive and green-sensitive silver halide emulsion layers, to give blue To filter out light that passes through the blue-sensitive layer can be.

If necessary, however, the selectively sensitized silicon halide emulsion layers can also be in a different order be arranged on the substrate. For example, the blue-sensitive layer that relates to the exposure side first layer, whereupon the red-sensitive layer and connect the green-sensitive layer.

The alkaline developing liquid can, for example, under Use of splittable containers of the US Pat. No. 2,543,181,

2 643 886, 2 653 732, 2 723 051, 3 056 492, 3 056 491 and

3 152 515 of the known type. However, it is also possible to supply the developing liquid in other ways, than from a split container. For example, the developing liquid can also be injected, for example by means of communicating members similar to kypodemic syringes, which can either be part of a camera or a camera cartridge.

In the case of a recording material according to the invention, a each silver halide emulsion layer having an image dye-providing compound or a layer associated therewith an image dye-providing compound from another silver halide emulsion layer and optionally one thereto associated layer with an image dye-forming layer

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Connection in the negative part of the recording material be separated by a separating layer, for example by a separating layer made of gelatin or calcium alginate or another layer of the type known from US Pat PS 3 421 892 is known or consists of layers of polymers, as described in more detail, for example, in FR-PS 2 028 236 and US-PS 2 992 104, 3 043 692, 3 044 873, 3 061 428, 3 069 263, 3,069,264, 3,121,011 and 3,427,158.

The silver halide emulsion layers advantageously exist of a gelatin recording material according to the invention containing silver halide emulsion layers. In advantageous Thus, the silver halide emulsion layers are about 0.6 to 6 microns thick. Are the compounds providing the image dyes in special layers, these consist of layers of a polymeric binder that is permeable to alkaline solutions, for example gelatin, with a layer thickness of about 1 to 7 microns. When using, permeable to alkaline solutions polymeric intermediate layers, for example gelatin layers, these are preferably about 0.5 to 5 microns thick.

The light-reflecting layers which are permeable to alkaline solutions and which can be present in recording materials according to the invention consist of an opacifying agent or an opacifying agent dispersed in a binder. The use of white light-reflecting layers has proven to be particularly advantageous because these provide an aesthetically pleasing background on which the transferred dye image can be viewed, and because such layers also have the optical properties required for the reflection of incident light are desirable. Typical suitable opacifying agents or opacifying agents are, for example, titanium dioxide, barium sulfate, zinc oxide, barium stearate, silver flakes, silicates, aluminum oxide, zirconium oxide, zirconium acetylacetate, sodium zirconium sulfate, kaolin, mica and mixtures thereof, these

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Compounds in various concentrations can be applied depending on the degree of haze or opacity desired. The opacifiers can be dispersed in a wide variety of conventional binders, e.g. in alkaline solutions permeable polymeric binders such as gelatin, polyvinyl alcohol and the like. The light-reflecting layer can also optionally contain optical brighteners, for example from the stilbene, Coumarin, triazine and / or oxazole type can be added. The opacity capacity of the light-reflecting layer can optionally be used can be increased by adding dark colored opacifiers, e.g. pH indicator dyes or carbon black, nigrosine dyes and the like. If necessary, such dark-colored opacifiers can also be accommodated in a special layer adjacent to the light-reflecting layer.

Advantageously, a recording material according to the invention can furthermore have a neutralizing layer, through which the stability of the transmitted image can be increased. Such a layer causes a reduction in the pH of the image layer from about 13 or 14 to at least 11 and preferably 4 to 8, within a comparatively short period of time after exposure to the developing liquid. To the For the production of such neutralizing layers, acids consisting of polymers can be used, for example they are known, for example, from US Pat. No. 3,362,819, or acids or metal salts in solid form, e.g. zinc acetate, Zinc sulfate and magnesium acetate such as are known from U.S. Patent 2,584,030. Such neutralizing or pH-reducing substances reduce the pH of the recording material after it has been developed and terminate the development process, preventing further transfer of the dye and stabilize the dye image obtained.

Advantageously, the recording material can furthermore have a so-called delay or control layer, which can be arranged in an advantageous manner over the neutralizing layer and which the pH reduction as a function of

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The rate at which alkali diffuses, controls or retards through this inert layer. Examples of such retardation or control layers are known from U.S. Patents 3,455,686, 3,421,893, 3,419,389, 3,433,633, 3,575,701, 3,785,815 and 3,856,522. Such a delay or control layer can also have a balancing effect on the various reaction rates within a wide temperature range and, for example, prevent a premature pH decrease if the action of the developing liquid takes place at temperatures above room temperature, for example at temperatures from 35 to 40 ^° C. In Advantageously, such retardation or control layers are about 0.2 to about 14 µm thick. Particularly advantageous results are obtained when the retardation or control layer consists of a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the developing liquid. Examples of such hydrolyzable polymers are polyvinyl acetate, polyamides and cellulose esters. Particularly good results are obtained when using mixtures of cellulose acetate and maleic anhydride copolyraeren, such as are known from FR-PS 2,290,698, for example.

To produce the image-receiving layer, it is customary to use compounds used to produce such layers are used, as long as they fulfill the task of the transferred To pickle or otherwise fix image dyes. It goes without saying that the structure of the particular image-receiving layer used depends on the type of dyes to be pickled. Is applicable to pickle acidic dyes, the image-receiving layer advantageously contains a basic polymeric mordant, e.g. a polymer «OQKXftttKOCffKgaJa * ^^ like

it is known, for example, from US Pat. No. 2,882,156. Further advantageous basic polymeric mordants for the production of image-receiving layers are, for example, from US Pat. No. 3,788,855, 3 758 445, 3 488 706, 3 639 357, 3 557 066, 3 709 690, 3 625 694, 3 898 088 and 3 859 096 are known. Other advantageous mordants for the production of the image receiving layers exist, for example

7 09 8 Uli 1 0 0 0

of poly-4-vinylpyridine, 2-vinylpyridine polymers of the U.S. Patent 2,484,430 and cetyltrimethylammonium bromide. Further advantageous mordants can be found in US Pat 3,271,148, 3,271,147 and 3,958,995 are known.

Further compounds which are advantageously suitable for the production of image-receiving layers are, for example polymeric compounds permeable to alkaline solutions, such as N-methoxymethyl polyhexylmethylene adipamide, partially hydrolyzed polyvinyl acetate and other compounds of the corresponding type. Particularly advantageous results are obtained when the image-receiving layer, which is preferably permeable to alkaline solutions is transparent and has a thickness of about 1 to about 5 µm.

The image-receiving layer can optionally also contain various additives, for example ultraviolet light-absorbing compounds to protect the transferred and stained dye images from fading due to the action of ultraviolet light , and also optical brighteners, for example those of the stilbene, coumarin, triazine or oxazole type as well finally stabilizers, for example chromanols and / or alkylphenols.

The alkaline developing liquid is different from the usually used to develop recording materials for the Dye diffusion transfer processes use developing fluids only by being an alkali metal salt of contains, üie developing liquid can thus consist of a conventional aqueous solution of an alkaline compound, for example an aqueous solution of sodium hydroxide, sodium carbonate or an amine, for example diethylamine, with a pH of at least about 11. In more advantageous Thus, the developing liquid contains a developing compound. Advantageously, the solution or developing liquid further contains a viscosity-increasing compound, for example a polymer of comparatively high molecular weight, e.g. a water-soluble ether that is inert to alkaline solutions, e.g. hydroxyethyl cellulose or an alkali metal salt the carboxymethyl cellulose, e.g., sodium carboxymethyl cellulose.

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Advantageously, the viscosity-increasing compound is present in a concentration of from about 1 to about 5% by weight, based on the weight of the developing liquid, and is increased the viscosity of the developing liquid to about 10,000 cPs to about 200,000 cps.

Optionally, as already stated, the developing liquid can contain an opacifying agent or an opacifying agent, e.g. TiO2 »soot and / or an indicator dye. Also can Indicator dyes containing ballast groups and dye precursor compounds in the recording material in a special one Layer be arranged on the exposure side of the photosensitive layers, these indicator dyes preferably are transparent during exposure and turn colored after contact with the alkali of the developing liquid or the layer, in which they are contained, make it opaque.

For the production of the recording materials according to the invention the conventionally known supports which are conventionally used for the production of photographic recording materials can furthermore be used. Typically exist the support of flexible films, e.g. of cellulose nitrate, cellulose acetate, poly (vinyl acetals), polystyrene, poly (ethylene terephthalate), polycarbonates, poly-α-olefins, e.g. polyethylene and polypropylene and the like. The layer support advantageously has a thickness of 0.05 to 0.23 mm. If appropriate, UV light-absorbing compounds can be used in the layer support be included. Such compounds can optionally also be applied to the support in the form of a special layer be.

The silver halide emulsions which can be used for the production of recording materials according to the invention are known emulsions, their Manufacture is known from the literature. Silver halide emulsions suitable for producing recording materials according to the invention are known, for example, from the literature "Product Licensing Index" Volume 92, December 1971, Publication 9232, Page 107, Paragraph I under the heading "Emulsion Types". the

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Emulsions can be chemically and spectrally sensitized, As for example from page 107, paragraph III under the heading "Chemical Sensitization" and from pages 108 to 109, Paragraph XV under the heading "Spectral Sensitization" of the cited literature stele is known. If necessary, can the emulsions be protected against the formation of fog and stabilized against loss of sensitivity during storage, for example using compounds, as described on page 107, paragraph V under the heading "Antifoggants and Stabilizers" of the cited literature are known. Finally, the emulsion layers can also contain development-modifying compounds, hardeners and / or Contain coating aids as described in pages 107-108, Paragraph IV under the heading "Development Modifiers", Paragraph VII under the heading "Hardeners" and Paragraph XII under the heading "coating auxiliaries" of the cited literature are known. The emulsion layers as well as other layers of the recording material can furthermore optionally contain plasticizers, binders and filter dyes contained, for example, from page 108, Paragraph XI under the heading "Plasticizers and equalizing agents", from Paragraph VII under the heading "Binder" and from page 109, Paragraph XVI under the heading "Absorption and filter dyes" are known. The silver halide emulsion layers and others Layers of the recording material can contain any further additives which were introduced by methods such as are known, for example, from page 109, paragraph XVII under the heading "Methods of addition" of the cited literature. Finally, the silver halide emulsion layers and other layers of the recording material according to the invention can be applied to the support, for example by methods be, as they are known, for example, from page 109, paragraph XVIII under the heading "Coating Process" of the cited literature.

The following examples are intended to illustrate the invention in more detail.

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example 1

First, a multilayer color photographic recording material with an integrated image receiving layer was thereby obtained produced that the layers listed below were applied in the specified order to a transparent poly (ethylene terephthalate) substrate, the specified

Concentrations given in each case relate to grams / m of substrate area, unless otherwise stated:

1) an image receiving layer made of 2.2 g of a copolymer from styrene and N-vinylbenzyl-N.N.N-trihexylammonium chloride and 2.2 g of gelatin; the weight ratio of the two monomers of the copolymer was 50:50;

2) a light reflective layer made of 22 g of titanium dioxide and 2.2 g Gelatin;

3) an opaque layer of 2.7 grams of carbon black and 1.7 grams of gelatin;

4) a cyan image dye providing layer of 0.54 g a compound of the following formula:

OH // \

CONH (CH ₂ ) ₄ O "

7 098 A 2/1000

dissolved in 0.27 g of diethyl lauramide and 0.73 g of gelatin;

5) a red-sensitive gelatin-silver chlorobromide emulsion layer of the inside image type composed of 1.1 g gelatin and 1.1 g silver, 8 g per mole of silver 2-sec.-octadecylhydroquinone-S-sulfonic acid and 1.5 g 1-acetyl-2- ^ p- ^ 5-amino-2- (2,4-di-t.-pentylphenoxy) benzamido7-phenyl7hydrazine per mole of silver as a fogging agent or nucleating agent;

6) an intermediate gelatin layer composed of 0.55 g gelatin and 1.1 g 2,5-di-sec-dodecylhydroquinone;

7) a magenta image dye providing layer of 0.65 g an image dye providing compound of the following formula:

OH

CH ₃ SO ₂ NH-

dissolved in 0.33 g of diethyl lauramide and 1.1 g of gelatin;

8) a green sensitive gelatin-silver chlorobromide emulsion layer of the inside picture type with 1.2 g gelatin and 1.1 g silver and 16 g 2-sec-octadecylhydroquinone-5-sulfonic acid per mole of silver and 1.5 g of 1-acetyl-2- ^ p- ^ S-amino-2- (2,4-di-tert-pentylphenoxy) benzamido7phenyl7hydrazine per mole of silver as a fogging agent or nucleating agent;

9) an intermediate gelatin layer composed of 0.55 g gelatin and 1.1 g 2,5-di-sec-dodecylhydroquinone;

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10) a yellow dye providing layer of 1.1 g of one yellow image dye-providing compound of the following formula:

CONH (CH ₂ ) ₄ O

N-N- \ I ^ =

CONHCH.

dissolved in 0.33 g of diethyl lauramide and 1.1 g of gelatin;

11) a blue-sensitive gelatin-silver chlorobromide emulsion layer of the inside image type with 1.1 g of gelatin and 1.1 g of silver, 8 g of 2-sec-octadecylhydroquinone-S-sulfonic acid per mole of silver and 1.5 g 1-Acetyl-2- ^ pi / 5-amino-2- (2,4-di-tert-pentylphenoxy) benzamide g7 ~ phenyl7hydrazine per mole of silver as well

12) a top layer of 0.54 g gelatin.

The silver halide emulsions used to produce the recording material consisted of direct positive emulsions with high internal sensitivity and low surface sensitivity of the type disclosed in U.S. Patent No. 3,761,276. the one cyan image dye and that one yellow image dye supplying compounds are known from published US patent application B-351,673. The compound providing a magenta image dye is known from US Pat. No. 3,932,380.

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The prepared recording material was then exposed to a multicolored test object with graduated density levels.

Various sections of the exposed material were then developed using the developing fluids indicated below. The developing fluids were in a splittable container. The liquids were between the uppermost layer of the recording material described and a cover sheet distributed in which from the recording material, the Cover sheet and the splittable container formed sandwiches were passed through the gap which was formed by two superposed pressure-exerting rollers. This made the The container with the developing liquid split open so that could distribute its contents between the recording material and the cover sheet. The cover sheet consisted of a transparent poly (ethylene terephthalate) backing with a neutralizing layer of polyacrylic acid and a control or retardation layer of cellulose acetate.

Two different developing liquids of the following composition were used to develop the recording materials. They were in the container A or the container B included.

Composition of the developing liquid Components Potassium hydroxide

4-methyl-4-hydroxymethyl-1-phenyl 3-pyrazolidone 5-methylbenzotriazole t-butyl hydroquinone

Sodium sulfate Potassium fluoride Carboxymethyl cellulose Topped up with water

Container A Container B (Comparison) 56 g 56 g 8.0 g 8.0 g 2.4 g 2.4 g 0.2 g 0.2 g 2.0 g 2.0 g - 6.0 g 200 g 200 g 51 g 51 g 1000 ml 1000 ml

In both cases, multicolored reproductions of the test template were made

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obtain. In the case of the test piece developed using the container A, however, 10 to 19 "spots" / « ^{2 were} noticeable on the observer side of the recording material. In contrast, in the case of the recording material which had been developed using the container B, no stains whatsoever were discernible.

Example 2

Further sections of the multilayer described in Example 1, Color photographic recording material were developed in a corresponding manner, but this time with containers for development C and O were used with other developing fluids.

Composition of the developing liquid

Container D

Components Container C 8th (Comparison) Potassium hydroxide 56 G ^ Methyl- ^ hydroxymethyl-i-phenyl- , 4 8 3-pyrazolidone 8th .2 g 5-methylbenzotriazole 2, .0 g t.-Buty! hydroquinone O ₁ G Sodium sulfite 2, S. soot 100 Carboxymethyl cellulose 51 to 1000 ml Oxalic acid - Topped up with distilled water

61 g

8 g

2.4 g 0.2 g 2.0 g

100 g 51 g

4.5 g 1000 ml

In both cases, multicolored reproductions of the test template were made obtain. On closer inspection of the pictures obtained, conditions were found which were similar to the conditions in the case of Example 1 were observed. This means that if the container C is used, a large number of "stains" was observed, whereas in the case of using the container D, no stains were noticeable.

Claims (1)

PATENT CLAIMS ,1. Photographic recording material for color diffusion transmission method with: a) at least one light-sensitive silver halide emulsion layer applied to a layer support, which contains an image dye-providing compound or is in contact with a layer comprising such a compound stands, b) an image receiving layer, c) a rupturable container with an alkaline developing liquid and d) a silver halide developer compound, characterized in that the alkaline developing liquid contains an alkali metal fluoride or alkali metal oxalate. 2. Recording material according to claim 1, characterized in that that it contains potassium fluoride or potassium oxalate. 3. Recording material according to one of claims 1 and 2, characterized in that a) the image-receiving layer is arranged between the support and the silver halide emulsion layer and that further b) the recording material has a transparent cover sheet the layer furthest from the substrate. 709842/1000 ORIGINAL INSPECTED 4. Recording material according to claim 3, characterized in that the cover sheet with a neutralizing layer and
a retardation or control layer is coated. 5. Recording material according to claims 1 to 4, characterized in that the splittable container with the alkaline
Developing liquid contains an opacifying compound and is arranged in the recording material in such a way that it
is split open during the development process when a force is applied to the container and is able to distribute its contents between the transparent cover sheet and the outermost layer furthest away from the support. 6. Recording material according to Claims 1 to 5, characterized in that the alkaline developing liquid is the
Alkali metal fluoride or alkali metal oxalate in a concentration of 0.01N to 0.5N contains. 7. Recording material according to Claims 1 to 6, characterized in that that the alkaline developing liquid has a pH of at least 11. 8. Recording material according to one of claims 1 to 7, characterized characterized in that it consists of: a) a light-sensitive part made of a transparent one Substrate on which are applied in the following order: an image receiving layer, one for alkaline solutions
permeable, light-reflecting layer, an opaque layer permeable to alkaline solutions, a red-sensitive layer
A silver halide emulsion layer which provides a cyan image dye contains remote, at least one ballast group having compound or with a layer with such a compound is in contact, a green-sensitive silver halide emulsion layer containing a magenta image dye-forming compound having at least one ballast group contains or is in contact with a layer with such a compound and a blue-sensitive silver halide emulsion layer which provides a yellow image dye, contains at least one ballast group having compound or with a layer with such a compound in contact stands; b) a transparent cover sheet over the blue-sensitive SiI-berhalogenide emulsion layer made of a transparent carrier a neutralizing layer applied thereon and a control or retardation layer; c) a splittable container with an alkaline developing liquid with a pH value of at least 11 with an opaque one making compound and an alkali metal salt of the specified type, which is able to distribute its contents between the transparent cover sheet and the blue-sensitive silver halide emulsion layer when exposed to pressure and d) a syllable halide developer compound. 9. Recording material according to one of Claims 1 to 8, characterized in that it contains at least one sulfonamido compound which has at least one ballast group as a compound providing an image dye and which, after oxidation, is capable of releasing a diffusible dye or a diffusible dye precursor compound upon exposure to alkali, and which corresponds to the following formula: {3 ~ ^(ballast) n-1 NHSO ₂ color 709842/1000 where mean: a) stain a dye or dye precursor residue; b) ballast an organic ballast group of such a molecular size and configuration that reduces the non-diffusivity of the compound in the recording material during the development process effected with an alkaline developing liquid at a pH of at least 11; c) G is a radical of the formulas -OR or -NHR., wherein R is a Represents hydrogen atom or a hydrolyzable radical and Rj represents a hydrogen atom or an alkyl radical with 1 to 22 Carbon atoms; d) Y those required to complete a benzene, naphthalene or 5- to 7-membered heterocyclic ring Atoms and e) η is a positive number of 1 or 2, where η ■ is 2, when G is a radical of the formula -OR, or when R. is a hydrogen atom represents or an alkyl radical of less than 8 carbon atoms. 10. Recording material according to one of claims 1 to 9, characterized characterized by having as the silver halide emulsion layer or layers those of the internal image type. 11. Recording material according to Claims 1 to 10, characterized in that that the image-receiving layer is arranged on a special transparent support which is above the outermost Layer or layers arranged on the opaque support with the silver halide emulsion layers. 12. Recording material according to claim 11, characterized in that the transparent layer support has a neutralizing layer, a control or delay layer and an image receiving layer. 7Θ9842 / 1000